Method for removing polymer films in the manufacture of aqueous compositions containing anionic amphiphilic polymers

ABSTRACT

This invention relates to a method to facilitate the removal of adherent polymeric films from a hard surface occasioned by the evaporation of solvent from compositions containing an anionic amphiphilic polymer, the method comprising incorporating a phosphate ester surfactant into the compositions, and washing the film from the surface to which it adheres.

FIELD OF THE INVENTION

[0001] This invention relates to a method to facilitate the removal ofadherent polymeric films from a hard surface occasioned by theevaporation of solvent from compositions containing an anionicamphiphilic polymer, the method comprising incorporating a phosphateester surfactant into the compositions, and washing the film from thesurface to which it adheres. In particular, the invention relates tocompositions containing an oxidizing agent; an anionic amphiphilicpolymer, and one or more phosphate ester surfactants, wherein saidcompositions are manufactured using stainless steel equipment.

BACKGROUND OF THE INVENTION

[0002] Oxidation dye precursors are colorless compounds that undergooxidative coupling in the presence of hydrogen peroxide to form coloredmolecules in the cortex of the fiber. Such precursors, namely, primaryintermediates and couplers, form the basis of cosmetic products forpermanently coloring hair.

[0003] In practice, oxidation hair dye products comprise two parts - ahair dye composition containing the dye precursors in a solvent system,and a developer composition that comprises an oxidizing agent,especially hydrogen peroxide. The first and second parts are mixedimmediately before application to the hair, at which time the precursorsare able to oxidatively couple owing to the presence of the oxidizingagent.

[0004] The final mixture as it is applied to the hair should be athickened liquid, preferably with a thixotropic viscosity, so that itstays put on the hair and does not run or drip during the period ofapplication. Many different thickening systems have been used for thispurpose. One class of thickening agents used for this purpose is anionicamphiphilic polymers, which can be included in the acidic hydrogenperoxide developer composition. At an acidic pH, the anionic amphiphilicpolymer is in its acidic form and the peroxide developer composition isa thin free flowing liquid. When the hair dye and peroxide developercompositions are mixed, the pH of the mixture is alkaline, the polymeris neutralized, and thickening is provided.

[0005] A number of patents have been issued covering the use of suchpolymers for thickening oxidation dyes, including the following: U.S.Pat. No. 4,776,855; U.S. Pat. No. 5,393,305; U.S. Pat. No. 5,376,146;U.S. Pat. No. 5,976,195; U.S. Pat. No. 5,988,295; U.S. Pat. No.6,074,439; and U.S. RE 33,786, all of which are incorporated byreference thereto.

[0006] Suitable known anionic thickening polymers include, e.g.,acrylates/beheneth-25 methacrylates copolymer, acrylates/steareth-20methacrylate copolymer, and steareth-10 allyl ether/acrylates copolymer.

[0007] This method of thickening oxidative hair dye productcompositions, i.e., the composition comprising a mixture of the firstpart hair dye composition and the second part developer composition, isadvantageous because the individual first part hair dye composition andsecond part developer composition can each be highly aqueous, i.e.,neither requires a high viscosity or specialized rheology. Accordingly,the resulting highly aqueous, thickened hair dye product composition ischaracterized by having high dyeing efficiency.

[0008] Disadvantageously, the anionic amphiphilic polymers tend to forman adherent polymeric film on the equipment (e.g., mixing tanks, storagetanks, etc.) used in manufacturing. These films are difficult to remove,requiring extensive cleanup procedures. For example, the use of a hotalkali solution has been used with some success. This is a particularlyvexing problem when stainless steel vessels are used for formulating,e.g., hydrogen peroxide compositions, because scrubbing such vessels canscratch the surface of the vessel, requiring that the vessel berepassivated before further use.

[0009] Developer compositions are known that contain varioussurfactants, e.g., polyethoxylated alcohols and phenols, such asceteareth-20 and nonoxynol-4, and anionic surfactants such as sulfatedcastor oil. Even when such surfactants are present in the anionicamphiphilic polymer -containing composition, the polymers tend to formadherent polymeric films and cleaning of the manufacturing vessels is aserious problem.

SUMMARY OF THE INVENTION

[0010] In accordance with the present invention, a method is provided tofacilitate the cleaning of hard surfaces, e.g., glass and metal,contacted by an anionic amphiphilic polymer during the manufacture ofcompositions containing such polymer and onto which a polymeric film hadformed. Film formation occurs during the manufacture of suchcompositions in which the anionic amphiphilic polymer is incorporatedwhen the solvent, typically water or a water-soluble organic solventmixture, has evaporated, leaving a polymer residue that adheres to thesurface. Because the compositions being manufactured invariably requiremixing, a solution or dispersion of the polymer will come into contactwith the walls of mixing vessels, and a film of the polymer is oftenformed before the vessel can be cleaned. Similarly, piping, agitators,storage tanks, pumps and other equipment commonly found in chemicalmanufacturing plants come into contact with the polymer while dissolvedor dispersed, following which the solvent evaporates leaving a residualpolymeric film. Moreover, spills as may occur during use of thepolymer-containing composition, e.g., when a polymer solution issloppily transferred to a vessel through a manhole, result in polymericfilms on exterior surfaces and on platforms, etc. This also may occurduring the manufacture of the anionic amphiphilic polymer itself,especially during storage of aqueous solutions or dispersions of theanionic polymer prior to sale.

[0011] We have found that, surprisingly, there is a markedly reducedtendency for the anionic amphiphilic polymers to form adherent polymericfilms on surfaces coming into contact with the polymer solutions anddispersions when a phosphate ester surfactant is present in the solutionor dispersion.

[0012] Polymers that form the difficult-to-remove films on hardsurfaces, especially metal surfaces, are anionic amphiphilic polymers,and most typically amphiphilic polymers based on acrylic acid. Theanionic amphiphilic polymer may be homopolymers or copolymers, and maybe linear, nonlinear or cross-linked.

[0013] The phosphate ester surfactant has the general structure

[0014] wherein R, R¹ and R² may be hydrogen, an alkyl of from 1 to about22 carbons, preferably from about 12 to 18 carbons, or an alkoxylatedalkyl of from 1 to about 22 carbons, preferably from about 12 to 18carbons, and having 1 or more, preferably from about 2 to about 25, mostpreferably 2 to 12, moles ethylene oxide, with the proviso that at leastone of R, R¹ and R² is an alkyl or alkoxylated alkyl as previouslydefined but 1 0 having at least 6 alkyl carbons in said alkyl oralkoxylated alkyl group.

[0015] In accordance with the present invention, there is provided amethod of cleaning surfaces, especially metal surfaces, in particulartanks, piping, agitators, pumps, and the like, used in the manufacture,transport and storage of anionic amphiphilic polymer-containingcompositions, in particular aqueous compositions, onto which saidpolymer has formed an adherent film, comprising incorporating aphosphate ester surfactant in said compositions, and washing the surfaceto substantially remove the polymeric film.

[0016] In another aspect of the present invention, aqueous compositionsare provided in which an anionic amphiphilic polymer is used as athickening agent, the aqueous compositions further comprising aphosphoric acid ester surfactant, whereby an adherent film of thepolymer occasioned by the evaporative drying of the composition onto ahard surface is more easily removed from said surface. Accordingly,suitable compositions comprise the anionic amphiphilic polymer; thephosphate ester surfactant, and water. In particular the presence of thephosphoric acid ester surfactant facilitates the removal of thecomposition from metal, most especially, stainless steel surfaces.

[0017] The present invention is most advantageous when stainless steelis used as the material of construction for the processing equipment infacilities manufacturing the anionic amphiphilic polymer-containingcompositions. This is because the aggressive removal of adifficult-to-remove film of the anionic amphiphilic polymer may damagethe stainless steel surface of equipment, especially mixing tanks. Suchdamage might require repassivization of the surface. Accordingly,incorporation of the phosphate ester surfactant in the anionicamphiphilic polymer-containing compositions to facilitate removal of anypolymeric film formed during or after process manufacture of thecomposition would reduce the tendency to damage the stainless steelsurface.

[0018] Such benefit is important in the manufacture of any productcomposition containing the film forming anionic amphiphilic polymer andespecially where stainless steel is employed. One such instance is inthe manufacture of oxidative hair dye products that comprise a hair dyecomposition of the oxidation dye precursors and a developer compositionthat contains an oxidizing agent, most typically hydrogen peroxide. Themanufacture of the developer composition may incorporate an anionicamphiphilic polymer where stainless steel is the construction materialof choice for hydrogen peroxide and many other oxidizing agents.

[0019] The present invention further concerns compositions containing afilm forming anionic amphiphilic polymer as a solution or dispersion inan appropriate solvent. In particular the present invention is drawn tosuch compositions containing an anionic amphiphilic polymer as anassociative-type thickening agent for oxidation hair dye products, thepolymer being present in the developer composition of that product.

DETAILED DESCRIPTION OF THE INVENTION

[0020] The present invention concerns a method of cleaning hard surfacessuch as glass or metal, in particular metal surfaces, and especiallystainless steel surfaces, onto which has formed a polymeric film of ananionic polymer occasioned by evaporation of the solvent in which thepolymer is dissolved or dispersed. According to the present invention,the incorporation of a phosphate ester surfactant during manufacture ofthe composition facilitates removal of the film.

[0021] In particular the method of the present invention concerns thecleaning of stainless steel surfaces, which can become damaged duringvigorous cleaning, which would then require the surface to berepassivated.

[0022] The Anionic Amphiphilic Polymers

[0023] The anionic amphiphilic polymers are usually polyacrylate orpolymethacrylate homopolymers and copolymers, and may be the alkalimetal or ammonium salts of such polymers. Illustrative of such polymersmay be mentioned, using the chemical nomenclature of the InternationalCosmetic Ingredient Dictionary and Handbook (Eighth Edition, 2000),incorporated herein by reference, the following:

[0024] Acrylates/Beheneth-25 Methacrylate Copolymer

[0025] Acrylates/C10-30 Alkyl Acrylate Crosspolymer

[0026] Acrylates/Ceteth-20 Methacrylate Copolymer

[0027] Acrylates/Ethylhexyl Acrylate Copolymer

[0028] Acrylates/Laureth-25 Methacrylate Copolymer

[0029] Acrylates/Palmeth-25 Acrylate Copolymer

[0030] Acrylates/Palmeth-25 Itaconate Copolymer

[0031] Acrylates/Steareth-50 Acrylate Copolymer

[0032] Acrylates/Steareth-20 Itaconate Copolymer

[0033] Acrylates/Steareth-20 Methacrylate opolymer

[0034] Potassium Acrylates/C10-30 Alkyl Acrylate Crosspolymer

[0035] Sodium Acrylates/C10-30 Alkyl Acrylates Crosspolymer

[0036] Steareth-10 Allyl Ether/ Acrylates C opolymer

[0037] In a preferred embodiment of the invention, the compositions ofthe present invention are acidic developer compositions containing anoxidizing agent for use in oxidation hair dye products. In acidiccompositions of course, the polymer salts would not be employed.

[0038] As used herein, the term “hair dye composition” refers to thecomposition containing primary intermediate and coupler oxidation dyesprior to admixture with the developer composition. The term “developercomposition” refers to compositions containing an oxidizing agent,especially hydrogen peroxide, prior to admixture with the hair dyeingcomposition. The term “hair dye product” or “hair dye system”interchangeably refers to the combination of the hair dyeing compositionand the developer composition before admixture, and may further includea conditioner product and instructions, such product or system oftenbeing provided packaged as a kit. The term “hair dye productcomposition” refers to the composition formed by mixing the hair dyecomposition and the developer composition.

[0039] The anionic amphiphilic polymer is used as a thickening agent insuch oxidative hair dye products. The anionic amphiphilic polymer isincorporated in the developer composition, which has an acidic pH. Atthe acidic pH, the polymer is dissolved or dispersed in the solvent,while at alkaline pH, and in the presence of a nonionic surfactant, thepolymer gels to thicken the composition. This occurs when the developercomposition is mixed with the hair dye composition to form the hair dyeproduct composition. See Technical Brochure FC-310a, Aculyn Thickenersand Stabilizers For Personal Care, Rohm and Haas (May 1996) and Cosmeticand Toiletries Manufacture Worldwide, “Acrylates/Beheneth-25Methacrylate Copolymer (Aculyn®28)”, V.10, p. 250-69, incorporated byreference.

[0040] Preferred anionic amphiphilic polymers for use as thickeningagents in the hair dye products are:

[0041] A) Acrylates/Beheneth-25 Methacrylate Copolymer, a copolymer ofthe ester of methacrylic acid and Beheneth-25 and one or more monomersof acrylic acid, methacrylic acid or one o their simple esters sold asAculyn 28 by Rohm and Haas;

[0042] B) Acrylates/C10-C30 Alkyl Acrylate Crosspolymer, a copolymer ofC₁₀-C₃₀ Acrylates and one or more monomers of acrylic acid, methacrylicacid or one of their simple esters crosslinked with an allyl ether ofsucrose or an allyl ether of pentaerythritol sold under the tradenamesCarbopol 1342, Carbopol 1382, Carbopol ETD 2020, Pemulen TR-1 andPemulen TR-2, all by B.F. Goodrich;

[0043] C) Acrylates/Cereth-20 Methacrylic Copolymer, a copolymer formedfrom the ester of methacrylic acid and Ceteth-20 and one or moremonomers of acrylic acid methacrylic acid or their simple esters;

[0044] D) Acrylates/Steareth-20 Methacrylic Copolymer, a copolymer ofthe ester of methacrylic acid and Steareth-20 and one or more monomersof acrylic acid, methacrylic acid or one of their simple esters soldunder the tradename Aculyn 22 by Rohm and Haas.

[0045] The Phosphate Ester Surfactant

[0046] The second essential component of the compositions of the presentinvention is the phosphate ester surfactant. By incorporating thephosphate ester surfactant into compositions containing the anionicamphiphilic polymer, it has been found that films of the anionic polymerformed on a hard surface when the solvent has evaporated are more easilyremoved.

[0047] Phosphate esters suitable for incorporation into the compositionsof the present invention have the formula

[0048] The phosphate ester surfactant has the general structure

[0049] wherein R, R¹ and R² may be hydrogen, an alkyl of from 1 to about22 carbons, preferably from about 12 to 18 carbons, or an alkoxylatedalkyl of from 1 to about 22 carbons, preferably from about 12 to 18carbons, and having 1 or more, preferably from about 2 to about 25, mostpreferably 2 to 12, moles ethylene oxide, with the proviso that at leastone of R, R¹ and R² is an alkyl or alkoxylated alkyl as previouslydefined but having at least 6 alkyl carbons in said alkyl or alkoxylatedalkyl group.

[0050] Monoesters in which R¹ and R² are hydrogen and R is selected fromalkyls of 10 to 18 carbons and alkoxylated fatty alcohols of 10 to 18carbons and 2 to 12 moles ethylene oxide are preferred. Among thepreferred phosphate ester surfactants, mention may be made of C12-16Pareth-6 Phosphate, C8-10 Alkyl Ethyl Phosphate, C9-15 Alkyl Phosphate,Ceteareth-2 Phosphate, Ceteareth-4 Phosphate, Ceteareth-5 Phosphate,Ceteareth-10 Phosphate, Ceteth-8 Phosphate, Ceteth-10 Phosphate, CetylPhosphate, C6- 10 Pareth-4 Phosphate, C12-13 Pareth- 10 Phosphate,C12-15 Pareth-2 Phosphate, C12-15 Pareth-3 Phosphate, C12-15 Pareth-6Phosphate, C12-15 Pareth-8 Phosphate, C12-15 Pareth-10 Phosphate, C12-16 Pareth-6 Phosphate, DEA-Ceteareth-2 Phosphate, DEA-CetylPhosphate, DEA-Oleth-3 Phosphate, DEA-Oleth-5 Phosphate, DEA-Oleth-10Phosphate, DEA-Oleth-20 Phosphate, Deceth-9 Phosphate, Deceth-4Phosphate and Deceth-6 Phosphate.

[0051] The Solvent

[0052] The compositions of the present invention are aqueous, and maycomprise water as the sole solvent, or may comprise water in combinationwith an essentially water-soluble organic solvent such as a mono- orpolyhydric alcohol. The compositions contain a sufficient amount ofsolvent so that the polymer is dissolved in the composition, or isdispersed in the composition. Preferably, water is the major componentof the solvent system. Preferably, the solvent constitutes from about 60to about 93% of the composition on a weight basis, most preferably fromabout 70 to about 85 % by weight.

[0053] Useful organic solvents are C₁ to C₆ alcohols and C₂ to C₈polyols. Especially useful alcohols for use in the solvent system of thepresent invention are ethyl alcohol, isopropyl alcohol and butylalcohol. Especially useful pohydric alcohols of the present inventionare ethylene glycol, propylene glycol, hexylene glycol, and glycerin.The alcohols typically comprise from about 0 to about 25% by weight ofthe composition.

[0054] Preferred Compositions

[0055] The preferred compositions of the present invention containhydrogen peroxide and are used as developer compositions in oxidativehair dye products.

[0056] The developer compositions comprise on a weight basis by weightof the composition: (a) from about 0.1 to about 10 of an anionicamphiphilic polymer, preferably 0.2 to 5%, most preferably 0.5 to 2.5%;(b) from about 1 to about 15% ti hydrogen peroxide, preferably 3 to 12,most preferably 3 to 9; (c) from about 0.1 to about 15% of a phosphateester surfactant, preferably 0.5 to 10, most preferably 0.5 to 5, and(d) solvent.

[0057] In the manufacture of the developer composition containing thehydrogen peroxide oxidizing agent, it is necessary to use stainlesssteel equipment, in particular stainless steel mixing tanks, to avoidcorrosion caused by the hydrogen peroxide.

[0058] Moreover, there is a tendency for the developer composition,which has an acidic pH, typically a pH from about 2.5 to about 6.5, tofoam during mixing, mixing being necessary to ensure homogeneity of thecomposition. As a consequence the side wall of the tank is coated with athin layer of developer composition, which dries rapidly when mixingends. The resulting polymeric film has proven to be quite difficult toremove and requires exposure to high pressure cleaning sprays, oftenwith highly alkaline cleaning products. Such treatment can cause damageto the stainless steel surface of the mixing tank, requiring it to berepassivated. This is true even though developer compositions typicallycontain a nonionic surfactant such as nonoxynol-2, nonoxynol-4, C₁₁-C₁₅Pareth-7, C₁₂-C₁₅ Pareth-9, and C₁₂-C₁₅ Pareth-3.

[0059] The incorporation of the phosphoric acid ester into the developercomposition has been found effective to reduce the tenacity of thepolymeric film to the side wall of the stainless steel.

[0060] The developer compositions contain any suitable oxidizing agent,particularly hydrogen peroxide and its addition compounds. Thus,suitable oxidizing agents include urea peroxide, the alkali metal andammonium salts of persulfate, perborate and percarbamate, especially thesodium salt, and melamine peroxide. The oxidizing agent is preferablypresent as a 3 to 12% (10 to 40 volume), most especially 6%, aqueoushydrogen peroxide solution. See e.g., deNavarre, The Chemistry andManufacture of Cosmetics, Vol. IV, p.847-50, (₂nd Edition, 1975).

[0061] The developer composition of the present invention may alsocontain, in addition to the anionic amphiphilic polymer, hydrogenperoxide, the phosphate ester surfactant, and water, one or moreadditional ingredients.

[0062] Accordingly, the developer composition may contain an acidifyingagent to provide an acid pH, preferably in the range of from about 3 toabout 5.5, most preferably from about 3.5 to about 4.5. At this pH thedeveloper composition preferably has an essentially Newtonian rheology,with a viscosity less than about 1000 cps, preferably less than about500 cps, most preferably less than 100 cps. Preferred polymer thickeningagents are Aculyn 22, and Aculyn 28 and mixtures thereof. Aculyn 22 and28 are associative, that is, their structures contain hydrophobic groupsthat build association with other hydrophobes present in theformulation, e.g., surfactants, particulates, dyes, etc.). The anionicamphiphilic polymers of the present invention may be combined with otherpolymeric thickeners that are not anionic or are not amphiphilic, e.g.,acrylates copolymer, a copolymer of two or more monomers of acrylicacid, methacrylic acid or one of their simple esters sold, e.g., underthe tradenames Aculyn 33 Polymer by Rohm and Haas; Salcare SC 81 byAllied Colloids, Luvimer 36D and Luvimer 30E by BASF, and Avalure AC115, Avalure AC 118 and Avalure AC 210 by B. F. Goodrich. Neutralizationby raising pH converts the polymeric thickeners of the present inventioninto clear viscous solutions. Such thickening occurs when the developeris admixed with the alkaline hair dye composition to provide a hair dyeproduct composition having a pH of from about 8 to about 11, preferablyfrom about 9 to 10.5. Advantageously, the Aculyn 22, Aculyn 28 andAculyn 33 polymers are peroxide stable. Most preferably a mixture of anassociative and non-associative polymer is employed. See U.S. Pat. No.5,376,146.

[0063] The developer composition may also include a surfactant otherthan the phosphate ester surfactant, which surfactant is selected fromthe group consisting of anionic, nonionic, and amphoteric (includingzwitterionic) surfactants. As used herein “surfactant” means asurfactant other than a cationic surfactant or a phosphate estersurfactant.

[0064] (Cationic surfactants, generally included as hair conditioningmaterials, are considered separately below.) Suitable surfactants, otherthan cationic surfactants, include fatty alcohol sulfates, ethoxylatedfatty alcohol sulfates, alkylsulfonates, alkylbenzensulfonates,alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols,ethoxylated fatty acids, ethoxylated alkylphenols, block polymers ofethylene and/or propylene glycol, glycerol esters, phosphate esters,fatty acid alkanol amides and ethoxylated fatty acid esters, alkylsulfates, ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates,methyl acyl taurates, acyl isethionates, alkyl ethoxy carboxylates,fatty acid mono- and diethanolamides.

[0065] The amount of surfactants in the developer compositions isnormally from about 0.1% to 30% by weight, preferably 1% to 15% byweight.

[0066] The developer composition may also include a conditioning agent.Materials suitable as conditioning agents include silicones and siliconederivatives; hydrocarbon oils; cationic surfactants that are monomericquaternary compounds, and quaternized polymers. Monomeric quaternarycompounds are typically cationic compounds, but may also includebetaines and other amphoteric and zwitterionic materials that provide aconditioning effect. Suitable monomeric quaternary compounds includebehentrialkonium chloride, behentrimonium chloride, stearalkoniumchloride, and many other compounds. See WO 98/27941 incorporated byreference. Quatenized polymers are typically cationic polymers, but mayalso include amphoteric and zwitterionic polymers. Useful polymers areexemplified by polyquatemium-4, polyquatemium-6, polyquaternium-7,polyquatemium-8, polyquaternium-9, polyquatemium-10, polyquaternium-22,polyquatemium-32, polyquatemium-39, polyquatemium-44 andpolyquatemium-47. Silicones suitable to condition hair are dimethicone,amodimethicone, dimethicone copolyol and dimethiconol. See also WO99/34770 published Jul. 15,1999, incorporated by reference, for suitablesilicones. Suitable hydrocarbon oils would include mineral oil.

[0067] Conditioners are usually present in the hair developercomposition in an amount of from about 0.01 to about 5% by weight of thehair dye composition.

[0068] Other optional ingredients include chelating and sequesteringagents such as EDTA, dispersing agents, penetrating agents, etc., inconcentrations effective to achieve their functional purpose.

[0069] Method of Cleaning Hard Surface

[0070] The polymeric films that are formed when the anionic amphiphilicfilm-forming polymer-containing compositions of the present inventionevaporate are removed by washing the surface with a cleaningcomposition. As used herein cleaning composition may include water as amedium to rinse the surface, but preferably is an aqueous solution of acleaning active. Cleaning actives may include alkali materials such assodium hydroxide, potassium hydroxide, ammonium hydroxide, (notpreferred because of odor), mono-, di- and triethanolamines; anionic,nonionic and amphoteric surfactants, including CP-1235 the phosphateester of the present invention, and compatible mixtures thereof.Preferably, the pH of the cleaning composition will be alkaline orneutral, most especially alkaline with a pH of from about 8 to about 10.A particularly useful cleaner is DuBois T-Off, a commercially availablecaustic-containing cleaner, in a 5 to 15%, preferably 10% aqueoussolution. The DuBois T-Off solution preferably is used at elevatedtemperature, especially from about 45 to 65° C. Preferably, the cleaningcomposition is sprayed under a moderate pressure of from about 15 toabout 65 psig, most preferably from about 20 to about 40 psig, until thefilm is removed. The application of the cleaning composition may beaccompanied by scrubbing with a broom, brush or other device. Scrubbingis not preferred where the surface being cleaned is stainless steel. Thecleaning time varies depending upon the nature of the cleaning solution,the temperature of cleaning, the time between cleanings, and the age ofthe film. Generally, the wash time is from one to several minutes to twohours in the case of a long-term film build-up. Usually, the film isremoved substantially, e.g., 90% or more of the film, in less than onehour.

[0071] The present invention is illustrated by the following examples.In this application the percentages are by weight of the totalcomposition unless other wise indicated.

EXAMPLES 1 to 4

[0072] Examples of four developer compositions containing 6.15% hydrogenperoxide (approximately 20 volume H₂O₂); an anionic amphiphilic polymerthickening agent, sufficient acidifying agent to provide a pH of 2.5-5,and varying concentrations of the phosphate ester surfactant laureth-4phosphate are set forth in Table 1 below. TABLE 1 Developer compositionscontaining anionic polymers and phosphate ester Ingredients Example 1Example 2 Example 3 Example 4 Water QS to 100 QS to 100 QS to 100 QS to100 Editronic acid 0.08 0.08 0.08 0.08 Disodium EDTA 0.04 0.04 0.04 0.04Aculyn 22/33¹ ² 5.0 4.0 — — (20/80 mixture) Aculyn 28³ — — 1.0 1.5Trilaureth-4 phosphate 2.5 4.0 4.0 5.0 Hydrogen peroxide 12.3 12.3 12.312.3 (50%)

[0073] The benefits of having phosphate ester in such developerscontaining anionic amphiphilic polymers is demonstrated by the followingexperiments to simulate the adhesion and removal of polymer films on ametal surface. An amount (0.5g) of developer solution is spread evenlyover a stainless plate ( 7 cm by 2 cm), and allowed to dry overnight atroom temperature to form a thick polymer residue. A thin polymer residueis produced when 0.2g of developer solution is used. The polymer residueis then rinsed under tap water (30° C) at a flow rate of 2liters/minute. Rinsing continues until the polymer film is removedcompletely from the plate. The time it takes to do so (or the rinsetime) is recorded, and the rinse times for different developercompositions are shown in Table 2 below. The data in Table 2 clearlydemonstrate the benefits of phosphate ester in a developer compositioncontaining Aculyn 28 or a mixture of Aculyn 22 and Aculyn 33. Thepolymer residues from the compositions without phosphate ester take morethan 120 seconds to be removed. Those that are formulated with phosphateester can be removed in much shorter time, ranging from 2 seconds toless than 30 seconds. TABLE 2 Effect of added phosphate on rinse timeRinse time Rinse time for thick for thin Developer compositions filmfilm A. With 5% Aculyn 22/Aculyn 33 in water >120 sec   >120 sec  (Example 1 less phosphate) B. With 5% Aculyn 22/Aculyn 33 in water  27sec  2.5 sec  plus 2.5% trilaureth-4 phosphate (Example 1) C. With 1%Aculyn 28 in water (Example 4 less >120 sec   >120 sec   phosphate) D.With 1% Aculyn 28 in water plus 5%  6.5 sec   2 sec trilaureth-4phosphate (Example 4)

[0074] While the invention has been illustrated in connection withoxidative hair dyeing developer formulation, the invention is applicableto any type of formulations in which anionic amphiphilic polymers areemployed and there is a possible problem with the formation ofundesirable film residues.

We claim:
 1. A method of cleaning a surface on to which a polymeric filmof an anionic amphiphilic polymer has formed upon evaporation of solventfrom an aqueous composition containing said polymer, the methodcomprising: (a) incorporating a phosphate ester surfactant in saidcompositions during its preparation, and (b) washing the hard surfacewith a cleaning composition to substantially remove said polymeric film.2. The method of claim 1 in which the surface is selected from the groupconsisting of glass and metal.
 3. The method of claim 2 wherein thesurface is metal.
 4. The method of claim 3 wherein the surface is steel.5. The method of claim 4 wherein the surface is stainless steel.
 6. Themethod of claim 5 in which the composition comprises hydrogen peroxideand has an acidic pH.
 7. The method of claim 1 wherein the anionicamphiphilic polymer is acrylate based.
 8. The method of claim 7 whereinthe polymer is selected from the group consisting of a)acrylates/beheneth-25 methacrylate copolymer; b) acrylates/C10-C30 alkylacrylate crosspolymer; c) acrylates/ceteth-20 methacrylic copolymer; d)acrylates/steareth-20 methacrylic copolymer, and mixtures thereof.
 9. Amethod of cleaning a stainless surface used in the manufacture, transferand storage of aqueous acidic compositions containing an anionicamphiphilic polymer and an oxidizing agent and to which surface saidpolymer has formed an adherent film, the method comprising (a)incorporating a phosphate ester surfactant of the formula I

wherein R, R¹ and R² may be hydrogen, an alkyl of from 1 to about 22carbons, or an alkoxylated alkyl of from 1 to about 22 carbons, andhaving from about 1 to about 25 moles ethylene oxide, with the provisothat at least one of R, R¹ and R² is an alkyl or alkoxylated alkyl aspreviously defined but having at least 6 alkyl carbons in said alkyl oralkoxylated alkyl group, and (b) washing the metal surface with acleaning composition to substantially remove said film.
 10. The methodof claim 9 wherein the anionic amphiphilic polymer is selected from thegroup consisting of a) acrylates/beheneth-25 methacrylate copolymer; b)acrylates/C10-C30 alkyl acrylate crosspolymer; c) acrylates/ceteth-20methacrylic copolymer; d) acrylates/steareth-20 methacrylic copolymer,and mixtures thereof.
 11. The method of claim 10 wherein the polymer isselected from the group consisting of acrylates/beheneth-25 methacrylatecopolymer, acrylate/steareth-20 methacrylate copolymer, and mixturesthereof.
 12. The method of claim 11 wherein said composition furthercomprises acrylates copolymer.
 13. The method of claim 12 wherein thepolymer is acrylates/steareth-20 methacrylate copolymer.
 14. The methodof claim 10 wherein the oxidizing agent is hydrogen peroxide.
 15. Themethod of claim 9 wherein the cleaning composition is an alkalinesolution having a pH of from about 8 to about
 10. 16. The method ofclaim 15 wherein the cleaning composition is applied under moderatepressure of from about 20 to 40 psig.
 17. A developer compositioncomprising on a weight basis by weight of the composition: (a) fromabout 1 to about 15% of a hydrogen peroxide oxidizing agent; (b) fromabout 0.1 to 15% by weight of a phosphate ester surfactant, (c) fromabout 0.1 to about 10% of an anionic amphiphilic polymer; and (c) water,said composition having an acidic pH, whereby polymeric films formedupon evaporation of said composition are more easily removed from asurface to which the film adheres.
 18. The composition of claim 17wherein the anionic amphiphilic polymer is selected from the groupconsisting of a) acrylates/beheneth-25 methacrylate copolymer; b)acrylates/C10-C30 alkyl acrylate crosspolymer; c) acrylates/ceteth-20methacrylic copolymer; d) acrylates/steareth-20 methacrylic copolymer,and mixtures thereof.
 19. The composition of claim 18 wherein thepolymer is selected from the group consisting of acrylates/beheneth-25methacrylate copolymer, acrylates/steareth-20 methacrylate copolymer,and mixtures thereof.
 20. The composition of claim 19 wherein saidcomposition further comprises acrylates copolymer.
 21. The compositionof claim 20 wherein the polymer is acrylates/steareth-20 methacrylatecopolymer.
 22. The composition of claim 18 wherein the pH is from about2.5 to about 6.5.
 23. The composition of claim 17 further comprising anorganic cosolvent selected from the group consisting of C₂ to C₆ mono-and polyhydric alcohols.
 24. The composition of claim 17 wherein thephosphate ester surfactant is selected from the group consisting ofC12-16 Pareth-6 Phosphate, C8-10 Alkyl Ethyl Phosphate, C9-15 AlkylPhosphate, Ceteareth-2 Phosphate, Ceteareth-4 Phosphate, Ceteareth-5Phosphate, Ceteareth-10 Phosphate, Ceteth-8 Phosphate, Ceteth-10Phosphate, Cetyl Phosphate, C6-10 Pareth-4 Phosphate, C12-13 Pareth-10Phosphate, C12-15 Pareth-2 Phosphate, C12-15 Pareth-3 Phosphate, C12-15Pareth-6 Phosphate, C12 -15 Pareth-8 Phosphate, C12 -15 Pareth-10Phosphate, C12-16 Pareth-6 Phosphate, DEA-Ceteareth-2 Phosphate,DEA-Cetyl Phosphate, DEA-Oleth-3 Phosphate, DEA-Oleth-5 Phosphate,DEA-Oleth-10 Phosphate, DEA-Oleth-20 Phosphate, Deceth-9 Phosphate,Deceth-4 Phosphate and Deceth-6 Phosphate.